Color photographic materials

ABSTRACT

A color photographic material suitable for an optical sound recording system having a photographic layer capable of forming silver images which remain without being bleached in the color photographic material in the bleach step after color development. The layer contains a bleach inhibitor having at least two oxyethylene groups.

United States Patent Sakai et a1.

COLOR PHOTOGRAPHIC MATERIALS Inventors: Tadao Sakai; Nobuo Yamamoto;

Masakazu Yoneyama; Masao Sawahara; Takeshi Hirose, all of Ashigara, Japan Fuji Photo Film Co., Ltd., Kanagawa, Japan Filed: May 15, 1973 Appl. No.: 360,507

Assignee:

Foreign Application Priority Data May 16, 1972 Japan 47-48451 US. Cl 96/22, 96/4, 96/60 BF, 96/74, 96/1145 Int. Cl. G03c 7/16, 003C 5/52, G03c 7/24 Field of Search 96/4, 60 BF, 22, 74, 55, 96/1145 References Cited UNITED STATES PATENTS 10/1956 Harriman 96/1145 X Primary ExaminerRonald H. Smith Assistant Examiner-Alfonso T. SiuroPico Attorney, Agent, or FirmSughru.e, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A color photographic material suitable for an optical sound recording system having a photographic layer capable of forming silver images which remain without being bleached in the color photographic material in the bleach step after color development. The layer contains a bleach inhibitor having at least two oxyethylene groups.

10 Claims, N0 Drawings 1 COLOR PHOTOGRAPHIC MATERIALS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates generally to color photographic materials and more particularly it relates to color photographic materials capable of recording sound images.

As sound-image recording systems for color photographic materials used for cine-projection or television, there is generally used an optical recording system or a magnetic recording system. The color photographic materials of the present invention are optical recording systems.

2. Description of the Prior Art The reproduction of sound by an optical recording system in color photographic print films, color photographic reversal films, color photographic reversal print films, etc., which are ordinarily used in the field of cine-projectionor in television systems, is carried out by converting sound signals recorded in the color films as patterns of varying density or area into optical signals, converting the optical signals into electric signals by means of a light acceptor, and then converting the electric signals into sound signals. In the sound reproduction system, photoelectric cells having various spectral characteristics are employed as the light acceptor. The photoelectric cell most commonly used for the purpose is a so-called S-l Type photoelectric cell having maximum spectral sensitivity at about 800 m.p.. in the infrared region [see, e.g., Adrin Cornwell Clyne,

Color Cinematography, 593 (1951)].

On the other hand, in conventional color photographic materials for a subtractive color process, the main absorptions of dyes formed by the coupling of the oxidation product of a developer, such as a pphenylenediamine, and color couplers are all in the visiblc region, which does not coincide with the spectral characteristics of the photoelectric cells used. Therefore, if optical sound recording is conducted only with coupled dye images, the sound output is quite weak and thus the utilization of such dye images for optical sound recording is impractical.

Accordingly, the reproduction of sound in color photographic materials has ordinarily been conducted by applying to the color photographic materials a processing which forms silver images or silver sulfide images in the sound track and utilizing the densities of the silver images or silver sulfide images in the infrared region for the reproduction of sound. In this case the infrared densities (transmittance densities) are usually about 1.0 to about L6.

The sound track in color photographic print films can be formed by the process shown in, for instance, the Journal of the Society of Motion Picture and Television Engineers;" Vol. 77, l 154 (1968). By this process the color image in image portions and the sound images or pattern in sound recording portions are simultaneously formed by color development in a color development bath. In the first fix bath, the unexposed silver halide is removed and in the bleach bath the developed silver formed in the development step is rehalogenated. Then, in a sound development step, a viscous sound developer is selectively applied to the sound track portions and the silver halide only at the sound track portions is converted into silver images. In the second fix bath the silver halide at the image portions is fixed and removed, and in the stabilization bath the dyes of the image portions are stabilized. The densities of the silver images in infrared. regions of the sound track thus formed are utilized for the reproduction of sound.

As mentioned above, in the formation of the sound track in color photographic films, forming silver images or silver sulfide images is required, i.e., the formation of such images is required in addition to forming dye images at image portions. As indicated above, the reason for forming such a sound track composed of silver or silver sulfide is that the spectral sensitivity characteristics of the photoelectric cells used. for the reproduction of sound provide a sensitivity maximum in the infrared region, while the colored dyes formed in color photographic materials in the color development step donot have sufficient density in such a long wave length region.

US. Pat. No. 3,715,208 discloses photographic elements having a auxiliary layer containing a silver bleach inhibitor. However, the silver bleach inhibitor described is clearly different from the compounds of the present invention having at least two oxyethylene groups and is inferior in effect.

SUMMARY OF THE INVENTION a bleach step after color development due to the presence of a bleach inhibitor having at least two oxyethyl- DETAILED DESCRIPTION OF THE INVENTION In general, a color photographic material is composed of a support having coated thereon multilayers of silver halide photographic emulsions, each sensitized in a different sensitive region. When such a color photographic material is imagewise exposed and then subjected to color development, dye images and silver images are formed. The silver images are then oxidized in a bleach process and further the oxidized silver images are removed from the color photographic material through a fix processing, whereby a color photograph consisting of dye image is obtained.

The color photographic material of this invention has a layer forming silver images which are not removed by such a bleach step and can provide a color photograph of dye images and silver images by ordinary color processing. The silver images are favorably utilized as a sound track for a color photographic material.

It has been found that when a developed silver image is contacted with a compound having at least two oxyethylene groups in the molecule, the silver is rendered unbleachable. Such a compound is hereinafter called in this specification a bleach inhibitor.

In one embodiment of this invention, the color photographic material has on a support a first silver halide emulsion layer containing a coupler capable of forming a yellow dye by reacting with the oxidation product of a color developing agent and having sensitivity to a first visible region, a second silver halide emulsion layer containing a coupler capable of forming a magenta dye by reacting with the oxidation product of a color developing agent and having sensitivity to a second visible region, a third silver halide emulsion layer containing a coupler capable of forming a cyan dye by reacting with the oxidation product of a color developing agent and having sensitivity to a third visible region, and a fourth silver halide emulsion layer containing a bleach inhibitor and having sensitivity to the visible, ultraviolet or infrared regions.

When a color photographic material as described above is exposed to an original and then colordeveloped, a yellow dye image and a silver image are formed in the first silver halide emulsion layer, a magenta dye image and a silver image in the second silver halide emulsion layer, a cyan dye image and a silver image in the third silver halide emulsion layer, and a silver image in the fourth silver halide emulsion layer. Then, when the color photographic material thus developed is subjected to bleach processing, the silver images formed in the first, second, and third silver halide emulsion layers are bleached but the silver image formed in the fourth silver halide emulsion layer remains unbleached by the action of the inhibitor contained in the emulsion layer. Thus, a color photograph having dye images and silver sound images is obtained.

The fourth silver halide emulsion layer may have sensitivity to any of visible, ultraviolet or infrared regions. However, in the case that the sensitive region of the fourth silver halide emulsion layer duplicates the sensitive region of the first silver halide emulsion layer, the second silver halide emulsion layer, on the third silver halide emulsion layer, it is desirable to reduce the sensitivity of the former below one-fourth, preferably below one-sixth, of the sensitivity of any of the latter. By selecting such a configuration, the silver image is formed only at the high density portions of the image in the fourth silver halide emulsion layer and the silver halide act as black print, which gives quite a desirable result for color reproduction.

1n the color photographic material of this invention, the silver halide emulsion layer containing the bleach inhibitor is at least one layer formed in addition to a blue-sensitive silver halide layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer for forming an ordinary color photographic material. ln a preferred embodiment of the color photographic materials of this invention, a bluesensitive silver halide emulsion containing a yellow dye-forming coupler, a red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler, a green-sensitive silver halide emulsion layer containing a magenta dye-forming coupler, and a green-sensitive silver halide emulsion layer containing the bleach inhibitor are formed on a support in the aforesaid order.

As earlier described, the bleach inhibitor containing layer can be sensitive to any of the ultraviolet, visible or infrared regions, Thus, the above passage merely defines one preferred embodiment of the invention.

In this case, the green-sensitive silver halide emulsion layer containing a magenta dye-forming coupler may be coated after the green-sensitive silver halide emulsion layer containing the bleach inhibitor is coated on the red-sensitive silver halide emulsion layer containing the cyan dye-forming coupler. Furthermore, in any 4 case the silver halide emulsion containing the bleach inhibitor can have spectral sensitivity to any of the ultraviolet, visible or infrared regions. in this embodiment only the order of the green-sensitive emulsion layer containing the magenta coupler and the greensensitive emulsion layer containing the bleach inhibitor is different from the earlier described embodiment.

Also, in another preferred embodiment of this invention, the light sensitive silver halide emulsion layers containing dye-forming couplers can be formed on the support in a different order than the above order. For instance, a red-sensitive emulsion layer containing a cyan dye-forming coupler, a green-sensitive emulsion layer containing a magenta dye-forming layer, a yellow filter layer containing colloidal silver or a yellow dye a blue-sensitive emulsion layer containing yellow dyeforming coupler, and a silver halide emulsion layer containing the bleach inhibitor are formed on support in the aforesaid order. [(1) Carey Lea type, (2) such as tartrazine and those described in US. Pat. No. 2,527,583)] The sound track image recording layer of the photographic material is only to record the sound track image. Latent images of the picture record should not be formed in the layer. Selective exposure of the sound recording and picture recording layers can be attained by the use of differential photographic speed or spectral sensitivity of the silver halide of these layers. For example, the sound recording silver halide emulsion layer can be sensitized to radiation to which the picture recording layers are at least partially insensitive, such as the infrared radiation or to the region of the relatively minimum sensitivity between two picture recording layers of adjacent spectral sensitivity, such as the region between the green and red sensitive layers. Alternatively, the sound recording layer can be slower than the picture recording layer of corresponding spectral sensitivity.

Practical examples of the bleach inhibitor used in this invention are illustrated below:

Compound 1. HO(CH CH O),,H (molecular weight:

about 1,000), Compound 2. HO(CH CH O),,H (molecular weight:

about 6,000), 7 Compound 3. HO(CH CH O),,H (molecular weight:

about 11,000), Compound 4. HO(CH CH O),,H (molecular weight:

about 20,000), Compound 5. C H COO(CH CH O), H, C0mp0und C7H15COO(CH2CH2O)15H, COmpOund C11H23COO(CH2CH2O)15H, Compound 8. C, H COO(CH CH O) H, C0mp0und C17H33COO(CH2CH2O)1()H, Compound 10. C H, COO(CH CH O) H,

Compound 11 O CnHmC O 0 (CH CH O)4-i-C\1Hn Compound 12 I 0 CHHHCO O (CHzCHgOM--CnHn,

Compound 13 O C |1He5C0O(CH1CH20)q 3C as,

Compound 14 O CUHMCOO (CH: C 1110 ea-iil-C H Compound 15 0 Compound 16. Compound 17. Compound 18. Compound 19. Compound 20. Compound 21. Compound22. Compound 23 Compound 24. Compound 25. Compound 26.

Compound 27 Compound 28 Compound 29 Compound 30 Compound 38 Compound 39 Compound 40 Compound 41 .2

Compound 42 Compound 43 Compound 44 Compound 45 Compound 31 (1341100,)

moan-Q cHzomomn,

Compound 36. CH O(CH CH O) H, COmpOund C2H50(CH2CH20')6H,

Compound 32 Compound 33 2.

Compound 34 (CHz 2 H doowmcmo} 04H,

m=15: ni mo Compound 46 Compound 47 Compound 48 H Compound 49 Compound 50 Compound 51 Compound 52 Compound 53 Compound 54 Compound 55 Compound 56 Compound 57 l CH2CH:O--H

A CnHaaC ON (CH CHrO I-I Compound 58 C 11 C5Hn- O CHzCIICH2O CH2CHCH2OH H la 0H Compound 59 CnHaaC O O CH2CHCHz-O CHz-?H-OH20H l H l27 OH Compound 60 N N o1 O CH2CH2O or I L J20 N N N\/N Compound 61 N N 01 O CHzCH2O G1 I jzo l 0N2. t Na Compound 62 The amount of the bleached inhibitor to be used in the color photographic material in this invention depends primarily upon the properties of the bleached inhibitor itself, but in general is in the range of about 1 X 10*g to l X 10 g, preferably 1 X 10 5 to 1 X g, per mole of the silver in the silver halide emulsion layer.

The amount of the bleach inhibitor may be varied with the halide composition and the grain size of the silver halide to be used in the layer.

The thickness for the sound track recording layer can vary greatly but is generally from about 0.5 to about 5 microns, preferably from 0.5 to 3 microns.

The mandatory components of the bleach inhibitor containing sound track recording layer of this invention are a silver halide, a hydrophilic colloid and the bleach inhibitor. A coupler can optionally be added thereto. Any silver halide emulsion conventionally used in a picture recording layer can be used in the sound track recording layer of this invention. It can comprise silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide or mixture thereof. it can be a negative developing out emulsion or a fogged direct positive emulsion. Gelatin or any conventional photographic hydrophilic colloid can be used as the vehicle for the silver halide in the sound track recording layer.

The sound track recording layer can also contain other addenda such as sensitizing dyes, hardeners for the hydrophilic colloid or coating aids. The selection of these and other addenda and the method of their incorporation in the silver halide emulsion of the sound track recording layer can be selected by the skilled artisan who wishes to prepare the emulsion considering the particular end use.

As preferred supports used for the color photographic materials of this invention, there are illustrated cellulose ester films such as cellulose nitrate films, cellulose acetate films, etc., polyester films such as polyethylene terephthalate films, etc., polyvinyl chloride films, polystyrene films, polycarbonate films, and the like. The support canbe freely selected from those in the art.

Any known photographic hydrophilic colloid can be used as a binder for the silver halide emulsion layers. For example, gelatin, albumin, gum arabic, agar-agar, cellulose derivatives such as alkyl esters of carboxy cellulose, hydroxy ethyl cellulose, carboxy methyl hydroxy ethyl cellulose and synthetic resins such as polyvinyl alcohol and polyvinyl pynolidone are preferred. These hydrophilic colloids are preferably also used as binders for layers other than the emulsion layers in the photographic materials, e.g., a protective layer, filter layer, intermediate layer, antihalation layer, subbing layer, backing layer etc.

The hydrophilic colloid used for various layers of the color photographic material of this invention is, profitably, hardened by a hardening agent such as an aldehyde hardening agent, a methylol. hardening agent, a 1,4-dioxane hardening agent, an aziridine hardening agent, an iso-oxazole hardening agent, a carbodiimide hardening agent, an active halogen hardening agent or an active vinyl hardening agent. Typical examples of such hardening agents are described in US. Pat. Nos.

3,100,704; 3,091,537; 3,321,313 and 3,543,292 and British Pat. Nos. 974,723; 1,167,207 and 994,869.

In this invention, there can be used any silver halide emulsion conventionally used in the field of photography, such as a silver bromide emulsion, a silver iodobromide emulsion, a silver chloroiodo-bromide emulsion, a silver chlorobromide emulsion, and a silver chloride emulsion.

1n the picture recording layers the preferred average grain size of the silver halide is from about 0.05 to about 1.5 microns, preferably, about 0.05 to about 1 microns.

1n the sound recording layer, the preferred average grain size of the silver halide is from about 0.05 to about 0.6 microns, preferably, about 0.05 to about 0.4 microns.

The weight ratio of silver halide to binder most suitably ranges from about 0.2 to about 20 (silver halide/- binder), preferably about 0.3 to about 5 in the picture recording and sound track recording layers. These values are not limitative. However excellent results are provided when these guidelines are followed.

Also, the so-called converted halide silver halide grains as described in U.S. Pat. No. 3,622,318 and British Pat. No. 635,841 can be used effectively in this invention.

The silver halide emulsions used in the color photographic materials of this invention can be chemically sensitized by active gelatin or a sulfur compound according to the process described in U.S. Pat. Nos. 1,574,944, 1,623,499 and 2,410,689. They can also be sensitized by a noble metal salt such as a palladium or a gold salt as described in U.S. Pat. Nos. 2,448,060, 2,399,083 and 2,642,361. Furthermore, they can be sensitized by a reducing agent such as a stannous salt as described in U.S. Pat. No. 2,487,850, or sensitized by a polyalkylene derivative. They can also be spectrally sensitizied by a cyanine by or merocyanine dye such as described in U.S. Pat. Nos. 2,519,001; 2,666,761; 2,734,900; 2,739,964 and 3,481,742.

The silver halide emulsions used in this invention can contain a stabilizer such as a mercury compound, an azaindene, etc., a plasticizer such as glycerin, etc., and a coating aid such as saponin, polyethylene glycol mono-lauryl ether, etc. Furthermore, they may contain an antistatic agent, a ultraviolet absorbent, a fluorescent brightening agent, etc.

In the present invention, every open chain type ketomethylene yellow-dye-forming color couplers can be effectively used. Typical examples of such yellow dyeforming couplers are benzoylacetoanilide color couplers, pivalylacetoanilide color couplers, etc.

Magenta dye-forming color couplers such as pyrazolone color couplers, indazolone color couplers, etc., are effectively used in this invention.

Furthermore, cyan dye-forming color couplers such as phenolic color couplers, naphtholic color couplers, etc., are effectively used in this invention.

Each of the couplers as mentioned above can have a coupling releasable or splitting off group at the active carbon atom at the coupling position thereof. It is pre- A great number of such couplers are known, but particularly desirable color couplers are color couplers forming yellow dyes having the absorption maximum in the wave length region of 420 460 mp. by reaction with the oxidation product of a color developing agent, color couplers forming magenta dyes having an absorption maximum in the wave length region of 520 570 mp. by reaction with the oxidation product of a color developing agent, and color couplers forming cyan dyes having the absorption maximum in the wave length region of 630 710 mp. by reaction with the oxidation product of a color developing agent.

Examples of non-diffusible couplers which can be incorporated into the picture recording silver halide emulsion layers of the photographic material are those described in U.S. Pat. Nos. 1,108,028; 2,186,849; 2,206,142; 2,343,702; 2,367,531; 2,369,489; 2,423,730; 2,436,130; 2,474,293; 2,600,788; 2,689,793; 2,728,658; 2,742,832; 2,808,329; 2,998,314; 3,046,129; 3,062,653; 3,265,506; 3,311,476; 3,408,194; 3,419,390; 3,419,391; 3,458,315;

3,476,563; 3,516,831 and 3,617,291 and British Pat. No. 1,183,515.

These color couplers are incorporated in the hydrophilic colloids for photographic materials by any known method. For instance, theycan be dispersed in hydrophilic colloids as a solution thereof in a high boiling organic solvent such as dibutyl phthalate, tricresyl phosphate, etc., containing, if desired, a low boiling organic solvent such as ethyl acetate, tetrahydrofuran, etc., according to the teachings of U.S. Pat. No. 2,322,027. When the color coupler has an acid group such as a carboxylic acid group or a sulfonic acid group, it is introduced into a hydrophilic colloid as an aqueous alkaline solution thereof.

In the sound track forming layer in this invention, it is desirable to obtain developed silver having a density as high as possible by a small amount of coating silver. Thus, it is profitable to incorporate in the sound track forming layer a compound having the action of accelerating development to give high density. As an example of a compound having such an action, there can be illustrated a compound capable of causing a coupling reaction with the oxidation product of a color developing agent, that is to say, a coupler The term coupler" in this case means a color coupler used for usual color photographic materials as well as a coupler (colorless coupler) which does not form a colored dye. Among these couplers, a coupler is particularly preferred which slightly diffuses when it is immersed in an alkaline developer and accumulates at or near the surfaces of developed silver as the unreacted coupler or as the coupling product.

Such a compound is considered to have the effect of protecting the silver image from the action of a bleaching agent and to reduce the bleaching speed. As an exferred that the color coupler used in this invention be provided with nondiffusing property by having a ballast ample of the coupler having such a property, there is illustrated a coupler having a diffusion resisting group, (for example, in coupler A:

. CII2CII Q2115 I provides this effect). vThe group preferably includes about six to about 12 carbon atoms and is attached directly, or through a bridging group such as an ether, es-

ter, or amide linkage, to the coupler molecule. Couplers other than the above can be provided with a desired diffusion resisting property by selecting the degrcc ofdissociation of couplers in an alkali and the hydrophilic property thereof. Practical examples of cou- 5 plcrs having such properties are illustrated below:

Coupler P (IH'I CONIHCIIQJO(CllrhClI:

Coupler Q OH I /(C 1193C:

CONII(C112)3O ClllgC ll Coupler R O ONH(CH2)3O (GHLOsCHa Coupler S V l figo ONH(CH2)a0 (CI-IzCHzOhCzHs Coupler T I @Oo ONH(CH2)6CH; Coupler U V 1 W ONH(CH2)1CH: Coupler V V (CHQaCHa CON\ Ds Hs Coupler W I (CH2)5CH3 CON\ (CHLOsCHJ Coupler X Cal-I13 O NCHzCHaC ONHC(]3H2 4Ho N C=O Such a coupler can be introduced into the sound track forming layer in the same way as in case of introducing the heretofore described color couplers Since those couplers are used for accelerating the silver image formation, the amount can vary greatly. The

amount of the couplers is generally about 2 X 10 to about 5 X mol, preferably 5 X 10" to 5 X l0 001 m A 04H C O O CHzCH 10 l CzHa -0 0 01120 ONH C u ler B l O CsHla Coupler C C O CHzC ONH O CsHn Coupler D C O CHzC ONH- 0 CIUHQI Coupler]? C O GHzC ONH CH3 0 CeHia Cou ler F p C2-C0 CH2CONH em 0 can" Coupler G C O CHzC ONH- Coupler H CHaC O CHzOONH- O CaHra Coupler I 40 0H30 0 CH2CONH- Coupler .T

CHaCOCH2CONH- Coupler K CHaCOCHzCONII- l O CrzHes Coupler L /CHa O2N\ C1oH2i Q0 0 01120 ONH-Q l Cl 0 CH3 Coupler M -oo CII:CONII@CON CsHn Coupler N CHaC O CHzC ONHCrzHzs Coupler O @00 011200 0 CmHzs mol, per mol of silver in the silver halide emulsion The infrared couplers described in the specification of Japanese Pat. application No. 94265/1971 can be used in the color photographic materials of this invention. The infrared coupler forms a dye having the absorption maximum at a wave length region longer than 725 m z by a coupling reaction with the oxidation product of a color developing agent. By utilizing the density of the dye thus formed, the density of the silver image of the optical sound track of this invention can be reduced, i.e., the amount of the silver to be coated can be reduced.

In conventional sound recording, the infrared density of the silver image in the sound track is substantially utilized, because photocells in projectors as are used have sensitivity in the infrared region. The infrared density is usually 1.0 to 1.6 in the sound track. When an infrared coupler is incorporated in an emulsion layer of the invention, an infrared dye is formed after the development. This infrared dye density contributes tothe sound track density together with the silver image in the sound track.

The color photographic material of this invention can be imagewise and sound-image wise exposed in any ordinary manner and then processed according to any ordinary color processing steps. The main steps of the color processing are color development, bleaching and fixing. Between those steps, water washing may be conducted, if necessary. After fixing, the color photographic material is washed and dried but it is desirable that the color photographic material be processed in a stabilization bath before drying.

As is known to those skilled in the art, photographic processing temperatures typically range from about C or less to 60 C or higher. Temperatures of about C or higher are suitablefor high speed processing procedures. Processing times for each processing step can widely vary, depending on the processing temperature, but usually range from several seconds to several minutes or more.

Typical examples of useful processing techniques are described in the Journal of the Society of Motion Picture and Television Engineers, volume 61, pages 667-701 (1953), and the British Journal of Photography, pages 122-123, 126 (1960).

Useful color developers include aqueous alkaline solutions containing a color developing agent. As the color developing agent, there is preferably used any known primary aromatic amine type dye-forming developing agent, for instance, phenylenediamines such as N,N-diethyl p-phenylenediamine, N-ethyl-N- hydroxyethyl p-phenylenediamine, N-ethyl-N- hydroxyethyl-2-methyl p-phenylenediamine, N-ethyl- N-methanesulfoneamide 'ethyl-3-methyl-4- aminoaniline, N,N-diethyl-2-methyl-pphenylenediamine, sulfates, hydrochlorides or sulfites thereof, and the like. See C.E.K. Mees and TH. James,

The Theory of the Photographic Process, pages 294-295 (The Macmillan Co, 1966), and US Pat. Nos. 2,592,364 and 2,193,015.

The color-developer may further contain additives as are ordinarily used in the art such as an alkali metal sulfitc, carbonate, bisulfite, bromide, iodide, benzyl alcohol, etc.

Any bleach solution containing a known bleach agent, such as a ferricyanide such as potassium ferricyanide and sodium ferricyanide, a bichromate such as potassium bichromate and sodium bichromate, etc., can be used in this invention. Also, any fix solution containing a known fixing agent such as sodium thiosulfate, potassium thiocyanide, etc., can be used.

Furthermore, the bleach step and the fix step can be conducted in one bath. This has been impossible in conventional processes requiring sound development. By using a blix bath in place of the bleach bath and the fix bath in this invention, the processing steps of the color photographic material of this invention can be further simplified and also the processing time can be reduced.

Solvents for silver halides as are used in blix solutions known to the art can all be used in the blix solutions for processing the color photographic materials of this invention. For instance, there are illustrated as such solvents for silver halides, a water-soluble thiosulfate such as sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, etc.; a water-soluble thiocyanide such as sodium thiocyanide, potassium thiocyanide, ammonium thiocyanide, etc.; a water-soluble organodiol fixing agent having an oxygen atom or a sulfur atom, such as 3-thia-l,5-pentanediol, 3,6-dithia-l,8roctanediol, 9-oxa-3,6,l2,15-tetra-thia-1,17-heptadecanediol, etc.; a water-soluble sulfur-containing dibasic acid or a water-soluble salt thereof, such as a ethylenebisthioglycolic acid, a sodium salt thereof, etc.; and an imidazolidinethion such as methylimidazolidinethion. etc.

Oxidizing agents for silver used in the blix solutions of the prior art can all be used in the blix solutions in this invention. Examples of such oxidizing agents are a water-soluble ferricyanide such as sodium ferricyanide. potassium ferricyanide, ammonium ferricyanide, etc.; a water-soluble quinone such as quinone, chloroquinone, methyl-quinone, etc.; a water-soluble ferric salt such as ferric chloride, ferric sulfide, ferric thiocyanide, ferric oxalate, etc.; a water-soluble cobaltic salt such as cobaltic chloride, cobaltic ammonium nitrate etc., and the like. Also, a multi-valent cation ofa watersoluble organic acid or an alkali metal complex salt of a water-soluble organic acid can preferbly be used as the oxidizing agent. The organic acids referred to include the compounds represented by the formulae wherein X represents a hydrocarbon group, an oxygen atom, a'sulfur atom, or =NR R R R R and R each represent an unsubstituted or substituted hydrocarbon group; and R represents a hydrogen atom or an unsubstituted or substituted hydrocarbon group.

Specific examples of the organic acids are malonic acid, tartaric acid, ethylmalonic acid, malic acid, fumaric acid, diglycolic acid, thioglycolic acid, ethyliminodipropionic acid, nitrotriacetic acid, ethylenediaminetetraacetic acid, aminotriacetic acid, ethylenedithioglycolic acid, dithioglycolic acid, and the like.

Specific examples of the multi-valent cations are ferric ion, cobaltic ion and cupric ion.

An iron-sodium complex salt of ethylenediaminetetraacetic acid is particularly useful as the bleaching agent.

In the blix bath in this invention, additives used for ordinary blix solutions can profitably be used. Examples of such additives are sodium sulfite, potassium bromide, potassium iodide, sodium iodide, polyalkylene oxide, 2-mercaptoimidazole, 3-mercapto-l ,2,4- triazole, dithioglycol, thiourea, ethylenethiourea, hy-

droxylaminc salts, p-aminophenol, ascorbic acid, semicarbazide, hydrazine, etc.

Specific practical examples ofa blix solution used for processing the color photographic materials of this invention are given below:

Bleaching agent below Sodium carbonate (mono-hydrate) g Boric acid 5g Sodium sulfite 5g Fixing agent below The blix solution is adjusted to have a pH of 6.0 and the volume is adjusted to 1.0 liter by adding water.

Several bleaching agent and fixing agent combinations for blix baths as described are shown below:

Blix bath Bleaching agent Fixing agent (a) Ferric sulfate (0.05 mol) Sodium thiosullatc disodium ethylcnediamine (0.6 mol) tctraacetatc (0.] mol) (11) Sodium iron (ill) ethylcnc- Sodium thiosulfate diaminc tetraacetic acid (0.] mol) Sodium thiosuifate (0.6 mol) 35 Typical bleach agents are discussed in detail in the Journal of the Society of Motion Picture and Television Engineers 61, 667-701 and US. Pat. No. 3,189,452;

typical fix agents in L.F.A. Mason Photographic Processing Chemistry, pages 187-188, Focal Press 1966); and

typical blix solutions in German Pat. Nos. 886,605 and 966,410, in British Journal of Photography, pages 122-123 and 126 (1966) and in US. Pat. 3,582,322. These references also disclose generally used proportions.

By developing the color photographic material of this invention in a color developer containing a color developing agent, the silver image necessary for recording a sound image is formed simultaneously with yellow, magenta, and cyan dyes for forming color images. Of course, silver images are also formed at the color image portions, but those silver images are easily bleached in the above-mentioned bleach bath or blix bath. However, the silver image formed in the emulsion layer containing the bleach inhibitor is not bleached in the bleach bath or blix bath and remains as the silver image.

Accordingly, since the sound image (silver image) is obtained by employing only an ordinary color developing process, an additional development step for forming a silver image for sound recording as in conventional prior art processes becomes unnecessary in this invention and thus the whole processing steps are greatly simplified by employing the color photographic material of this invention. That is to say, by employing the color photographic material of this invention, socalled silver sound development as in conventional systems is unnecessary.

Also, according to the present invention, a sound track of silver images is provided. Therefore. there is the advantage, in the case of using the color photographic material of this invention, that it is not accompanied by a reduction in density by the action of light. 5 heat, or moisture, which is ordinarily observed in a recording band made of an organic dye having absorption at the infrared region.

Furthermore, in the case where a color photographic material has therein a yellow filter layer containing yellow colloidal silver or an antihalation layer containing black colloidal silver, those colloidal silvers are rehalogenated in the bleaching step and the halogenated silvers are further developed in the sound development. Hence, in such a case, the conventional sound development is unapplicable. On the other hand, be-

cause in the present invention such an additional sound development is unnecessary, it becomes possible to use colloidal silver in the color photographic materials.

The invention will now be further illustrated in detail 20 by several examples of preferred specific embodiments.

EXAMPLE 1 The opposite surface of a cellulose acetate film support to the surface having an antihalation layer containing carbon black was coated with a subbing layer and on the subbing layer was coated a. coating composition containing a silver iodobromide emulsion containing 1.2 mol percent of iodide and 0.05 mol of silver and yellow coupler, i.e., a dispersion prepared by dispersing a-(Z-methyl-benzoyl)-3-[a-(2,4-dirtert-amylphenoxy)acetamide]-acetoanilide, of the formula -oooHlooNH- CHa in a mixture of dibutyl phthalate and ethylacetate to form a blue-sensitive layer. On the blue-sensitive layer was formed a gelatin intermediate layer and on this layer was coated a coating composition containing silver chlorobromide emulsion (0.06 mol of silver) containing 30 mol percent of bromide: and a cyan coupler, l-hydroxy-4-chloro-N-hexanedecyl-N-(2-cyanoethyl)- 2-napthamide, of the formula CIllnCHnCN C ON\ OwHaa formula i on s (I A e C-CII=(JII-=CII--CH=G\ to form a red-sensitive layer. On the red-sensitive layer Ammums Coming silver coupler gelnuntbmdcr) thickness was formed a gelatin intermediate layer and on the m.- Inygr re /m? LZ /nfi n /m 4,; layer was further coated a coating composition con- W" u' s/ in/in LRg/m as ,1

. 6 l f magenta layer 1.1g/nr' log/m 3.0g/m"' 4.5 p

turning a silver chlorobromide emulsion (0.0 mo o sound mick Inn/mt tt- [A silver) containing 35 mol percent of bromide and a dlS- 5 g t u g'g v V D perslon of magenta couplers, l-(2,6-dichloro-4- 3,"; ism/mol silver methylphenyl)-3-{3-[a-(2,4-di-tert-amy1phenoxy) butr viu c mu mat- Sum ylamldoibenzamido} 's'pyrazolone' of the formula "dc mrmmg 180 mg/mol silver ratio of two magenta couplers 1/1 by weight.

z t C1 H 02:11 CONH H2OCO\ (no. u- 4 4H3 m ggy 7 (IJONH-C=N 1 d 1 (2,4,fi qi hl h bg-{3[ QA-di-t t- Each of the Samples 1, 11, 111 and 1V thus prepared arylamylphenoxy)-butylamido]benzamido}-5- was exposed to a tungsten lamp (2,854 K) through an pyrazolone f h f l ultraviolet absorbing filter transmitting light having c 11 or N- -01 i rHno) ONH- =N this silver halide emuslion having been spectrally sensiwave lengths longer than about 400 mu, a .yellow filter tized so that it had its sensitization maximum at about transmitting light having wave lengths longer than 555 mu by a sensitizing dye of the formula about 500 mu, and a silver wedge. The intensity was 100,000 lux for 1/100 second. The filters used for the exposure were ones usually employed for the exposure o E2115 0 of color print films.

Each of Samples 1, 11, 111 and IV thus exposed was N processed according to process A or. process B as i l shown below. The density of the infrared region of the mgmcmsofi Hm films (narrow band, peak about 88 mp. conventionally used for measuring sound track density) thus obtained so H was measured using a Status S-58 filter by means of a Macbeth TD-206 A-type densitometer. The results are shown in Table 1.

to form a green-sensitive layer. 40 Process A Thereafter, a dispersion of liquid paraffin in an aque-' ous gelatin solution was coated on the green-sensitive; processing Step Temperature Time layer to form a protective layer. The color photo-I {ac-path 2d7C 1(5) secongs 115 O- SCCOTI S graphic print film thus prepared was designated as} Color development do 5 minutes Sample I. l and 20 see. A color photographic print film was also prepared by gf 38' the same way as above except that a sound track formw 40 sgconds ing layer was formed between the green-sensitive layer 31 2 3 m and the protective layerin Sample I by coating a coati i mg composition containing a silver chlorobromide development 0 emulsion (0.06 mol of silver) containing 80 mol perfix 3 3 cent of bromide and a dispersion of 6.45 g of the aforewash 5 Second; said coupler A in 1.3 ml. of dibutyl phthalate. 1.5 g of smhllllflllon 10 Seconds the aforesaid compound 42 as a bleach inhibitor, and the sensitizing dye used in the green-sensitive layer of. the Sampe 1. The film was designated Sample 11.

A color photographic print film was further prepared in the same way as in the case of preparing sample 11 except that the dispersion of coupler A was omitted.

The compositions of the processing baths used in the 'above processing were as follows:

Pre-bath solution:

The film was designated Sample 111. l Water 800 ml Furthermore, a color photographic prmt.fi1m was Sodium carbonate(mono-hydrate) l().(lg also prepared in the same way as in the case of prepar- Sodlum Sulfate (anhydrous) g Water to make 1 liter ing Sample 11 except that compound 42 and the disper- Color developer; sion of coupler A were omitted. The film was deslgg t h t h h t 28 0 turn exame ap osp a e g nated Sample Anhydrous sodium sulfite 4.0 g The coated amount of silver 1n the sound track formtnlno-S-diethylammotoluene hydrochloride 3.0 g ing layers of Samples 11 to IV was 1.5 g/m and the gggli'ghf g gm gg 38g amounts of all components present were as follows: water to make Tu red density was obtained in Sample II.

EXAMPLE 2 A color photographic print film was prepared in the same way as in the case of preparing Sample II in Ex- 21 22 f I h d d I ample 1 except that a black antihalation'layer contain- Fira t t 1111011 IX 600 m] mg colloidal silver and gelatin was formed on the sub- Sodium thiosulfatc (5-hydrate) 240 g bing layer of Example 1 in place of forming the antiha- Sulfile 3:85 lation layer containing carbon black on the back sur- Boric acid 60 g 5 face of the support. The film was designated Sample V. Potassium alum -9 g The amounts of coating for this layer were: Water to make 1 liter Bleach solution:

Water 800 ml Potassium bromide 20.0 g colloidal silver gelatin thickness Potassium bichromate 5.0 g 10 antihalation 0.5g/m 2g/m 2 Potassium alum 0.0 g layer Sodium acetate (hi-hydrate) 3.0 g wafiallaccui mid g g The sample was exposed in the same way as in Exammr I I a a Soun il tievelop er: ple 1 and sub ected to process B in Example 1 wherein. (Liquid A) however, the pre-bath and the immediately following Water 600 ml h d Anhydrous sodium sumle 400 g was were omitte and then the infrared density of the N-m cthyl-o-uminophcnol sulfate 28.8 g developed film was measured in the same way as in Ex- Sodiuiii hydroxide g Hydrouquinone 40.0 g ample l. The results are shown in Table 2. Liquid B) 300 l Water Tragacanth gum g 2 Table 2 Denatured alcohol 10 ml 0 (Liquid C) Ethylenediamine (70%) +7 I ml Sample V Liquid A was mixed with liquid B, and just before use Process B liquid C was added together with water to the mixture I f d density v to make the total volume 1.0 liter. Stabilization bath:

As shown above, good results as in Example 1 were w obtained in the color photographic material of this infig (37%) vention having an antihalation layer containing colloi- Polyethylene glycol (MW. 400) 40% aqueous soln. 5 ml dal silver. water to make l liter EXAMPLE 3 Process B Each of Samples 1, ll, [[1, IV, and V in Examples 1 and 2 was exposed as in Example l and then processed Processing step Temperature Time v according to Process C shown below, and then the inafligg 5 frared density measured as in Example 1. The results Color development do. 5 minutes and are shown in Table 20 seconds Wash do. l5 seconds First fix do. 1 minute Wash do. seconds 40 PIOCESS C Bleach do. 3 minutes Wash do. 1 minute Second fi 2 minutes Processing step Temperature Time w 5 minutes Pre-bath 27C 10 seconds Stabilization do. 10 seconds Wash 15 F Color do. 5 minutes and g development 20 seconds Wash do. l5 seconds The compositions of the processing baths used in the Blix do. 4 minutes rocess were the same as those in Process A sh wn wash 2 mules p i 0 Stabilization do. 10 seconds above.

Table 1 Sample I ii iii lV Process A B A B A B A B Infrared LiLliSlly 1.95 0.04 2.73 1.83 2.69 (1.63 2.30 0.04

From the results shown in Table 1, it can be under- The composition of the blix bath was as follows. stood that sufficient infrared density was not obtained in Samples l and IV without the application of the sound development, while high infrared density was ob-. tained by an ordinary color development or without z ggg fg g 340g sound development in Samples ii and III, which .were sodium c rb (mono-hydrate) 11.0 g the color photographic materials of this invention con- 55 1h, If t 18-? g taining the bleach inhibitor. In particular, a high infraj 'g l a e mi,

The compositions of the processing baths other than the blix bath were the same as those in aforesaid process A.

23 1 24 Table 3 Table Sample I ll lV Sample Vll Vlll Process C C C C 5 Process I B C B C I fr d Infrared density 1.90 1.93 2.03 1.95 density 0.06 1.95 0.72 0.10 L82 From the results shown in Table 3, it can be understood that Samples ll, ll], and V, which were color photographic materials of this invention, provided high infrared density even if they were processed in the blix bath without applying sound development, while Sample l, which was a conventional type color photographic material, and Sample lV, having a sound track forming layer but containing no bleach inhibitor, gave low infrared density.

EXAMPLE 4 A color photographic print film was prepared in the sameway as in case of preparing Sample ll in Example 1 except that 5.5 g of the aforesaid coupler P was used in place of the coupler A and L5 g of the aforesaid compound 44 was used in place of compound 42. The film was designated Sample VI. Sample VI was exposed, processed, and the infrared density was measured according to the manner of Examples 1 and 3.

EXAMPLE 6 Color photographic films were prepared in the same way as in Example 5 except that 1.5 g of each of the aforesaid compounds 10, 40, 43, 45, 51, and 59 was used in place of compounds 42 or 44 and 2.7 g of the aforesaid coupler K was used in place of coupler A or coupler P. The films were designated Samples IX, X, XI, Xll, XIII and XIV, respectively. These samples were exposed, processed, and infrared density was measured according as in Example 4. The results are shown in Table 6. The results show that high infrared The results are shown in Table 4. 3 density was obtained in each case.

Table 6 Sample IX X x1 x11 x111 XIV Bleach Supress Hi 43 45 SI 5) ing agent Process B C B C B C B C B C B C Infrared density 2.20 1.90 2.10 1.95 2.20 1.86 2.30 2.20 2.20 1.99 1.311 2.20

Table 4 EXAMPLE 7 Color photographic films were prepared as in Exam- Sample ple 6 except that 1.5 g of the above-mentioned com- Pmcess B C pound 42 was used as the bleach suppressing agent and 2.7 g of the above-mentioned coupler F and 2.6 g of the Infrared denmy coupler Q were, respectively, used as the coupler. The

As shown above, high infrared density was obtained with Sample VI, which was a color photographic material of this invention. In addition, when the sample was processed in an ordinary bleach bath containing potassium bichromate as an oxidizing agent for silver, a high infrared density was similarly obtained.

EXAMPLE 5 films were designated Samples XV and XVI. Those samples were exposed, processed, and infrared density measured as in Example 4. The results are shown in Table 7. As is shown in the table, high infrared density was obtained in each case Samples ll, ill, and V were exposed and processed as in Example 4 and the infrared density measured. To determine the change in density of the recording band during storage, the samples were stored for 14 days under the conditions of 60 c, and 70% relative humidity, and then the infrared density was measured again. The changed percentages of density before and after the storage test are shown in Table 8.

Table 8 Sample 11 ll l V Process B C B C B C Changed percentage of infrared 99 I 100 100 99 I03 density halide emulsion layer containing a yellow dye-forming,

coupler, atleast one red-sensitive emulsion layer containing a cyan dye-forming coupler, at least one greensensitive emulsion layer containing a magenta dyeforming coupler, and at least one silver halide emulsion layer containing a bleach inhibitor having at least two oxyethylene groups, said silver halide emulsion layer substantially not being capable of forming a dye image for picture recording.

2. The color photographic material as set forth in claim 1 wherein said silver halide emulsion layer containing the bleach inhibitor is formed adjacent to the green-sensitive emulsion layer.

3. The color photographic material as set forth in claim 1 wherein said silver halide emulsion layer containing the bleach inhibitor is formed adjacent to an intermediate layer adjacent to the green-sensitive emulsion layer.

4. The color photographic material as set forth in claim 1 wherein said silver halide emulsion layer containing the bleach inhibitor is formed adjacent to the blue-sensitive emulsion layer.

5. The color photographic material as set forth in claim 1 wherein said silver halide emulsion layer is formed adjacent an intermediate layer adjacent to the blue-sensitive emulsion layer.

6. The color photographic material as set forth in claim 1 wherein said silver halide emulsion layer con taining the bleach inhibitor further contains a coupler.

7. The color photographic material as set forth in claim 1 wherein said silver halide emulsion layer containing the bleach inhibitor has a sensitivity lower than.

one-fourth of the sensitivity of the silver halide emulsion layers for forming dye images.

8. The color photographic material as set forth in claim 1 wherein said color photographic material is a color photographic print film.

9. A process of forming dye images and silver images in the color photographic material as set forth in claim 1 comprising subjecting said color photographic material to exposure, color development, bleaching and fixmg.

10. The process as set forth in claim 9 wherein said bleach and said fix are conducted in a mono-bath sys- 

1. A COLOR PHOTOGRAPHIC MATERIAL COMPRISING A SUPPORT HAVING THEREON AT LEAST ONE BLUE-SENSITIVE SILVER HALIDE EMULSION LAYER CONTAINING A YELLOW DYE-FORMING COUPLER, AT LEAST ONE RED-SENSITIVE EMULSION LAYER CONTAINING A CYAN DYEFORMING COUPLER, AT LEAST ONE GREEN-SENSITIVE EMULSION LAYER CONTAINING A MAGNETA DYE-FORMING COUPLER, AND AT LEAST ONE SILVER HALIDE EMULSION LAYER CONTAINING A BLEACH INHIBITOR HAVING AT LEAST TWO OXYETHYLENE GROUPS, SAID SILVER HALIDE EMULSION LAYER SUBSTANTIALLY NOT BEING CAPABLE OF FORMING A DYE IMAGE FOR PICTURE RECORDING.
 2. The color photographic material as set forth in claim 1 wherein said silver halide emulsion layer containing the bleach inhibitor is formed adjacent to the green-sensitive emulsion layer.
 3. The color photographic material as set forth in claim 1 wherein said silver halide emulsion layer containing the bleach inhibitor is formed adjacent to an intermediate layer adjacent to the green-sensitive emulsion layer.
 4. The color photographic material as set forth in claim 1 wherein said silver halide emulsion layer containing the bleach inhibitor is formed adjacent to the blue-sensitive emulsion layer.
 5. The color photographic material as set forth in claim 1 wherein said silver halide emulsion layer is formed adjacent an intermediate layer adjacent to the blue-sensitive emulsion layer.
 6. The color photographic material as set forth in claim 1 wherein said silver halide emulsion layer containing the bleach inhibitor further contains a coupler.
 7. The color photographic material as set forth in claim 1 wherein said silver halide emulsion layer containing the bleach inhibitor has a sensitivity lower than one-fourth of the sensitivity of the silver halide emulsion layers for forming dye images.
 8. The color photographic material as set forth in claim 1 wherein said color photographic material is a color photographic print film.
 9. A process of forming dye images and silver images in the color photographic material as set forth in claim 1 comprising subjecting said color photographic material to exposure, color development, bleaching and fixing.
 10. The process as set forth in claim 9 wherein said bleach and said fix are conducted in a mono-bath system. 